WO2013156129A1 - Polymers containing substituted oligo-triarylamine units and electroluminescence devices containing such polymers - Google Patents

Description

 Polymers containing substituted oligo-triarylamine units and electroluminescent devices containing these polymers

The present invention relates to polymers comprising substituted oligo- ^1- triarylamine repeating units, preferably bis-triarylamine

Repeating units, processes for their preparation and their use in electronic or optoelectronic devices, in particular in organic electroluminescent devices,

so-called OLEDs (OLED = Organic Light Emitting Diodes). Moreover, the present invention also relates to organic

Electroluminescent devices containing these polymers.

In electronic or optoelectronic devices, in particular in organic electroluminescent devices (OLED)

Components of different functionality needed. In OLEDs, the different functionalities are usually in different layers. In this case one speaks of multilayer OLED systems. These multilayer OLED systems include, but are not limited to, charge injecting layers, e.g. electron and

hole injecting layers, charge transporting layers, e.g. Electron and hole-conducting layers, as well as layers on, the

contain light-emitting components. These multilayer OLEDs

Systems are typically made by sequential layer-by-layer application.

If several layers of solution are applied, care must be taken to ensure that an already applied layer after it has been dried is not destroyed by the subsequent application of the solution to produce the next layer. This can be achieved, for example, by rendering a layer insoluble, for example by crosslinking. Such methods are e.g. in EP 0 637 899 and WO 96/20253.

In addition, it is also necessary, the functionalities of the individual layers of the material side so to each other

to agree that the best possible results, e.g. regarding

CONFIRMATION COPY Lifespan, efficiency, etc. can be achieved. In particular, the layers which directly adjoin an emitting layer, in particular the hole transporting layer (HTL = Hole Transport Layer), have a significant influence on the properties of the adjacent layers

emitting layer.

One of the objects of the present invention was therefore in the

Providing compounds which can be processed from solution on the one hand and, on the other hand, when used in electronic or optoelectronic devices, preferably in OLEDs, and in particular in their hole transport layer, improve the properties of the device, i. especially the OLED lead.

Surprisingly, it has been found that polymers which have oligotriarylamine repeat units of which at least one aryl group is substituted in the ortho position, in particular when used in the hole-transporting layer of OLEDs, lead to a significant increase in the lifetime of these OLEDs.

The subject matter of the present application is thus a polymer which has at least one structural unit of the following formula (I):

dabei ist

is there

Ar ¹ to Ar ⁵ at each occurrence, each same or different, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;

i and j are each 0 or 1, the sum (i + j) = 1;

R for each occurrence are identical or different H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each containing one or more radicals R ¹ may be substituted, wherein one or more non-adjacent CH ₂ groups by R ¹ C = CR ¹ , C ^ C,

Si (R ¹ ) ₂ , C = O, C = S, C = NR ¹ , P (= O) (R ¹ ), SO, SO _2l, NR ¹ , O, S or CONR may be substituted and where one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy or

Heteroaryloxygruppe having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or a Diarylaminogruppe, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, or a crosslinkable group Q, wherein two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic and / or benzoannelliertes ring system ; R is the same or different at each occurrence H, D, F or a

aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and / or a heteroaromatic hydrocarbon radical having 5 to 20 carbon atoms, in which also one or more H atoms may be replaced by F; where two or more substituents R ^{1 can} also together form a mono- or polycyclic, aliphatic or aromatic ring system; and

n = 1, 2 or 3, preferably 1 or 2 and more preferably, the dashed lines being bonds to adjacent ones

Represent structural units in the polymer,

characterized in that in the case i = 0 and j = 1, Ar ² and / or Ar ⁴ is in each case substituted in at least one, preferably in one of the two ortho positions, with Ar ⁶ , Ar ^{6 being} a mono- or polycyclic, aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms which may be substituted by one or more R radicals and

in the case i = 1 and j = 0, Ar ⁴ and / or Ar ^{5 are} each substituted in at least one, preferably in one of the two ortho positions, with Ar ⁶ , wherein Ar ^{6 is} a mono- or polycyclic, aromatic or

heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals.

The structural unit of the formula (I) accordingly has 2 bonds

adjacent structural units in the polymer. Where i = 1 and j = 0, or i = 0 and j = 1.

The structural unit of the formula (I) thus corresponds to one of the following two structural units:

oder

or

In the case of the formula (1-1), the substituent Ar ^{6 may} be arranged either only on Ar ² or Ar ⁴ or on Ar ² and Ar ⁴ .

In the case of the formula (I-2), the substituent Ar ^{6 may} be arranged either only on Ar ⁴ or Ar ⁵ or on Ar ⁴ and Ar ⁵ .

Ar ⁶ can either be linked directly, that is to say via a single bond, with Ar ² and / or Ar ⁴ or Ar ⁴ and / or Ar ⁵ or else via a linking group X. Thus, the structural unit of the formula (I) preferably has the structure of the following formulas (I-1a), (1-1b), (I-2a) and (I-2b):

wobei Ar¹ , Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ und R die oben angegebenen

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and R are as indicated above

To be able to assume meanings

m = 0, 1, 2, 3 or 4,

X = CR ₂ , NR, SiR ₂ , O, S, C = O or P = O, preferably CR ₂ , NR, O or S, and

r = 0 or 1, preferably 0.

Particularly preferred are the formula (1-1 a) and (b). In a further embodiment of the present invention, the at least one structural unit of the formula (1-1) of the polymer according to the invention is characterized in that Ar ² and / or Ar ⁴ is in each case substituted by Ar ⁶ in one of the two ortho positions, and Ar ² and / or Ar ⁴ is additionally linked in each case with Ar ⁶ in the meta position adjacent to the substituted ortho position.

The structural units of the formula (1-1) thus preferably have the structure of the following formulas (1-1 c) and (1-1 d):

wobei Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, R und m die oben angegebenen

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , R and m are as indicated above

To be able to assume meanings

n = 0, 1, 2 or 3,

X = CR ₂ , NR, SiR _2> O, S, C = O or P = O, preferably CR ₂ , NR, O or S, and

p and q are each 0 or 1, the sum being (p + q) = 1 or 2, preferably 1.

In the present application, the term polymer is to be understood as meaning both polymeric compounds, oligomeric compounds and dendrimers. The polymeric compounds of the present invention preferably have from 10 to 10,000, more preferably from 10 to 5000, and most preferably from 10 to 2000 structural units (i.e., repeating units). The oligomeric compounds according to the invention preferably have 3 to 9 structural units. The branching factor of the polymers is between 0 (linear polymer, without branching points) and 1 (fully branched dendrimer).

The polymers of the invention preferably have one

Molecular weight M _w in the range from 1000 to 2,000,000 g / mol, particularly preferably a molecular weight M _w in the range from 10,000 to 1,500,000 g / mol, and very particularly preferably a molecular weight M _w in the range from 50,000 to 1,000,000 g / mol on. The determination of the molecular weights M _{w are} carried out by GPC (= gel permeation chromatography) against an internal polystyrene standard.

The polymers according to the invention are either conjugated, partially conjugated or non-conjugated polymers. Preference is given to conjugated or partially conjugated polymers.

The structural units of the formula (I) can be incorporated according to the invention into the main or the side chain of the polymer. Preferably, however, the structural units of formula (I) are incorporated into the main chain of the polymer. When incorporated into the side chain of the polymer, the structural units of formula (I) may be either mono- or bivalent, i. they have either one or two bonds to adjacent ones

Structural units in the polymer.

"Conjugated polymers" within the meaning of the present application

Polymers which in the main chain mainly sp ² -hybridized (resp.

optionally also sp-hybridized) contain carbon atoms, which may also be replaced by correspondingly hybridized heteroatoms. In the simplest case, this means alternating presence of double and single bonds in the main chain, but also polymers with units such as a meta-linked phenylene are to be considered as conjugated polymers for the purposes of this application. "Main" means that naturally (involuntarily) occurring defects which gation to Konju ^{'interruptions} result, do not invalidate the term "conjugated polymer." as the conjugated polymers also polymers are having a conjugated backbone and non-conjugated side chains. Furthermore, in the present application also referred to as conjugated when in the main chain, for example arylamine units,

Arylphosphineinheiten, certain heterocycles (ie conjugation of N, O or S atoms) and / or organometallic complexes (ie conjugation via the metal atom) are located. The same applies to conjugated dendrimers. In contrast, units such as simple alkyl bridges, (thio) ether, ester, amide or imide linkages are clearly defined as non-conjugated segments. In the present application, a partially conjugated polymer is to be understood as meaning a polymer which contains conjugated regions which are separated from one another by nonconjugated sections, targeted conjugation breakers (for example spacer groups) or branchings, for example in which longer conjugated sections in the main chain are replaced by non-conjugated segments. Conjugated portions are interrupted, or containing longer conjugated portions in the side chains of a non-conjugated in the main chain polymer. Conjugated and partially conjugated polymers may also contain conjugated, partially conjugated or non-conjugated dendrimers. The term "dendrimer" is to be understood in the present application, a highly branched compound consisting of a

multifunctional center (core) is built on that in one

regular structure branched monomers are bound, so that a tree-like structure is obtained. Both the center and the monomers can assume any branched structures consisting of purely organic units as well as organometallic compounds or coordination compounds. As used herein, "dendrimer" is to be understood as meaning e.g. by M. Fischer and F. Vögtle (Angew Chem, Int Ed., 1999, 38, 885).

The term "structural unit" in the present application means a unit which, starting from a monomer unit which has at least two, preferably two, reactive groups, is incorporated by reaction under compounding as part of the polymer backbone, and linked thereto present in the produced polymer as a repeat unit.

The term "mono- or polycyclic aromatic ring system" in the present application means an aromatic ring system having 6 to 60, preferably 6 to 30 and particularly preferably 6 to 24 aromatic ring atoms, which does not necessarily contain only aromatic groups but in which also several aromatic units by a short non-aromatic unit (<10% of H

different atoms, preferably <5% of the atoms other than H), such as, for example, an sp ³ -hybridized C atom or O- or N- Atom, a CO group, etc., can be interrupted. They shall example, systems such as ^9,9' spirobifluorene, 9,9-diarylfluorene and 9,9-dialkylfluoren, be taken to mean aromatic ring systems. The aromatic ring systems may be mono- or polycyclic, ie they may have one ring (eg phenyl) or several rings which may also be condensed (eg naphthyl) or covalently linked (eg biphenyl) or contain a combination of fused and linked rings , Preferred aromatic ring systems are, for example, phenyl, biphenyl,

 Terphenyl, [1, 1 ': 3', 1 "] terphenyl-2'-yl, quarterphenyl, naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene In the present application, the term "mono- or polycyclic, heteroaromatic ring system" is understood as meaning an aromatic ring system having 5 to 60, preferably 5 to 30 and particularly preferably 5 to 24 aromatic ring atoms, one or more of these atoms a heteroatom is / are. The "mono- or polycyclic heteroaromatic ring system" does not necessarily include only aromatic

But may also be replaced by a short non-aromatic moiety (<10% of the atoms other than H, preferably <5% of the atoms other than H), such as an sp ³ -hybridized carbon atom, or O- or N- Atom, a CO group, etc., be interrupted. The heteroaromatic ring systems may be mono- or polycyclic, ie they may have one or more rings, which may also be fused or covalently linked (eg pyridylphenyl), or contain a combination of fused and linked rings. Preference is given to fully conjugated heteroaryl groups.

Preferred heteroaromatic ring systems are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, tetrazole, furan, thiophene, selenophen, oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, 1, 2,3- Oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,3-triazine, 1, 2,4 , 5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-tetrazine, or multi-ring groups such as carbazole, indenocarbazole, indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine,

Naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthroxazole,

Phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, Benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene,

Isobenzothiophene, dibenzothiophene, benzothiadiazothiophene or

Combinations of these groups.

The mono- or polycyclic, aromatic or heteroaromatic ring system may be unsubstituted or substituted. Substituted means in the present application that the mono- or polycyclic, aromatic or heteroaromatic ring system has one or more substituents R.

R is preferably identical or different at each occurrence H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , Si (R ¹ ) _3> B (OR ¹ ) ₂ , C (= 0) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R, S (= O) ₂ R ¹ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thio-alkoxy group with 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R ¹ wherein one or more non-adjacent CH ₂ groups are represented by RC = CR ¹ , C ¹ -C ⁴ , Si (R ¹ ) ₂ , C = O, C = S, C = NR ¹ , P (= O) (R ¹ ) , SO, SO ₂ , NR ¹ , O, S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy or heteroaromatic radical aryloxy group having 5 to 60 aromatic ring atoms which may be substituted by one or more R, or an aralkyl or

Heteroaralkylgruppe having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a Diaryl- amino group, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a crosslinkable group Q; Two or more radicals R may also together form a monocyclic or polycyclic, aliphatic, aromatic and / or benzoannulated ring system.

R is more preferably identical or different at each occurrence H, D, F, Cl, Br, I, N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more R radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ¹ C = CR ¹ , C = C, Si (R ¹ ) ₂ , C = O, C = NR ¹ , P (= O) (R ¹ ), NR ¹ , O or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by F, Cl, Br or I, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may each be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an aralky L or heteroaralkyl group having 5 to 30 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or a Diarylaminogruppe, Diheteroaryl- amino group or Arylheteroarylaminogruppe having 10 to 20 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a crosslinkable group Q; two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic and / or benzoannulated ring system. R is most preferably the same at each occurrence

different H, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkynyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R ¹ , wherein one or more non-adjacent CH ₂ groups is represented by R ¹ C = CR ¹ , CsC, C = 0, C = NR ¹ , NR ¹ , O or CONR ¹ may be replaced, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group having 5 to 20 aromatic ring atoms which may be substituted by one or more R groups, or an aralkyl or heteroaralkyl group having 5 to 20 aromatic ring atoms which may be substituted by one or more R ¹ groups, or a diarylamino group, diheteroaryl amino group or arylheteroarylamino group having 10 to 20 aromatic ring atoms, which may be substituted by one or more radicals R, or a crosslinkable group Q; two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic and / or benzoannulated ring system.

Preferred alkyl groups having 1 to 10 carbon atoms are shown in the following table:

R ¹ is preferably identical or different at each occurrence, H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and / or a heteroaromatic hydrocarbon radical with 5 up to 20 C atoms, in which also one or more H atoms may be replaced by F; In this case, two or more substituents R can also be a mono- or polycyclic, aliphatic or

form aromatic ring system.

R ¹ is more preferably identical or different at each occurrence, H, D or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, an aromatic and / or a heteroaromatic hydrocarbon radical having 5 to 20 carbon atoms; in this case, two or more substituents R ^{1 can} also be a mono- or polycyclic, aliphatic or

form aromatic ring system.

R is very particularly preferably identical or different at each occurrence, H or an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, an aromatic and / or a heteroaromatic hydrocarbon radical having 5 to 10 carbon atoms.

In a preferred embodiment, the at least one

Structural unit of the formula (1-1 a), (1-1 b), (1-1 c) or (1-1 d) selected from the structural units of the following formulas (II), (III), (IV), ( V), (VI), (VII), (VIII) and (IX):

- 15-

- 15-

wobei Ar¹, Ar³, Ar⁵, Ar⁶, R, m, n und X die oben angegebenen Bedeutungen annehmen können, und

wherein Ar ¹ , Ar ³ , Ar ⁵ , Ar ⁶ , R, m, n and X may have the meanings given above, and

p = 0, 1, 2, 3, 4 or 5.

In a particularly preferred embodiment, the structural units of the formulas (II) and (III) are selected from the structural units of the following formulas (IIa) and (IIIa):

can accept.

Examples of preferred structural units of the formulas (IIa) and (IIIa) are shown in the following table: - 17-

wherein Ar ¹ , Ar ² , R, m, n and p may have the meanings given above, and

k = 0, 1 or 2.

In a further particularly preferred embodiment, the structural units of the formulas (IV) and (V) are selected from the structural units of the following formulas (IVa) and (Va):

wherein Ar ¹ , Ar ³ , Ar ⁵ , R, m, n and X may have the meanings given above.

Examples of preferred structural units of the formulas (IVa) and (Va) are shown in the following table:

-21 -

-21 -

wobei Ar¹, Ar², R, m, n und p die oben angegebenen Bedeutungen annehmen können.

where Ar ¹ , Ar ² , R, m, n and p can assume the meanings given above.

In yet another particularly preferred embodiment, the structural units of the formulas (VI) and (VII) are selected from the

Structural units of the following formulas (Via) and (VIIa):

---- Ar¹ N— Ar³ N— Ar⁵ ---- wobei Ar¹, Ar³, Ar⁵, R, m, n und X die oben angegebenen Bedeutungen annehmen können.

- Ar ¹ N - Ar ³ N - Ar ⁵ ---- wherein Ar ¹ , Ar ³ , Ar ⁵ , R, m, n and X may have the meanings given above.

Examples of preferred structural units of the formulas (Via) and (VIIa) are shown in the following table:

wobei Ar¹ , Ar², R, k, m, n und p die oben angegebenen Bedeutunge annehmen können.

where Ar ¹ , Ar ² , R, k, m, n and p can assume the meanings given above.

In a very particularly preferred embodiment, the structural units of the formulas (IIa) and (IIIa) are selected from the structural units of the following formulas (IIb) and (IIIb):

wobei Ar³, R, m und p die oben angegebenen Bedeutungen annehmen können.

where Ar ³ , R, m and p can assume the meanings given above.

Examples of preferred structural units of the formulas (IIb) and (IIIb) are shown in the following table:

wobei R, k, m, n und p die oben angegebenen Bedeutungen annehmen können. 30

where R, k, m, n and p can assume the meanings given above.

In a further very particularly preferred embodiment, the structural units of the formulas (IVa) and (Va) are selected from the structural units of the following formulas (IVb) and (Vb):

where Ar ³ , R, X, m and n can assume the meanings given above.

wobei R, X, k, m, n und p die oben angegebenen Bedeutungen annehmen können, und

wherein R, X, k, m, n and p can assume the meanings given above, and

s = 1 to 20, preferably 1 to 0, is.

In yet another very particularly preferred embodiment, the structural units of the formulas (VIa) and (VIIa) are selected from the structural units of the following formulas (VIb) and (VIIb):

where R, X, m and n can assume the meanings given above.

Examples of preferred structural units of the formula (VIb) and (VIIb) are shown in the following table:

wobei R, X, k, m, und n die oben angegebenen Bedeutungen annehmen können.

where R, X, k, m, and n can assume the meanings given above.

In the formulas (IIb) to (VIIb), the dashed lines represent the

They can be arranged independently of one another, identically or differently, in the ortho, meta or para position, preferably in the ortho, meta or para position, particularly preferably in the meta position. or para position, and most preferably in the para position. The proportion of structural units of the formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII) or (IX) in the polymer is in the range from 1 to 100 mol%.

In a first preferred embodiment, the polymer according to the invention contains only one structural unit of the formula (I), (II), (III), (IV), (V),

(VI), (VII), (VIII) or (IX), i. their proportion in the polymer is 100 mol%. In this case, the polymer according to the invention is a homopolymer.

In a second preferred embodiment, the proportion is

Structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) in the polymer in the range from 50 to 95 mol% , particularly preferably in the range of 60 to 95 mol%, based on 100 mol% of all copolymerizable monomers which are contained in the polymer as structural units, ie that the polymer according to the invention in addition to one or more structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) further, from the structural units of the formula (I), (II), (III), ( IV), (V), (VI), (VII), (VIII) and (IX) has various structural units.

In a third preferred embodiment, the proportion is

Structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) in the polymer in the range from 5 to 50 mol% , particularly preferably in the range from 25 to 50 mol%, based on 100 mol% of all copolymerizable monomers which are contained in the polymer as structural units, ie that the polymer according to the invention in addition to one or more structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) further, from the structural units of the formulas (I), (II), (III), ( IV), (V), (VI), (VII), (VIII) and (IX) different

Has structural units.

These, from the structural units of the formulas (I), (II), (III), (IV), (V), (VI),

(VII), (VIII) and (IX) various structural units are, inter alia, those as disclosed in WO 02/077060 A1 and in WO 2005/014689 A2 and listed extensively. These are considered via quotation as part of the present invention. The others For example, structural units can come from the following classes:

Group 1: units containing the hole injection and / or

 Affect hole transport properties of the polymers;

Group 2: units containing the electron injection and / or

 Influence the electron transport properties of the polymers;

Group 3: Units that are combinations of individual units of the group

 1 and group 2 have;

Group 4: units which the emission characteristics so far

 change that electrophosphorescence instead

 Electrofluorescence can be obtained;

Group 5: units that transition from singlet to

 Improve triplet state;

Group 6: Units indicating the emission color of the resulting

 Influence polymers;

Group 7: units typically used as polymer backbone

 (Backbone) can be used;

Group 8: units containing the film morphology and / or the

 influence rheological properties of the resulting polymers.

Preferred polymers according to the invention are those in which

at least one structural unit has charge transport properties, i. contain the units from group 1 and / or 2.

Structural units from group 1, the hole injection and / or

Have hole transport properties, are, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, Phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiin, carbazole, azulene, thiophene, pyrrole and furan derivatives, and other O, S or N containing heterocycles.

Preferred structural units from group 1 are the structural units of the following formulas (1a) to (1 q):

 where R, k, m and n can assume the meanings given above. In the formulas (1a) to (1q), the dashed lines represent possible

Bonds to the adjacent structural units in the polymer. If in the formulas two dashed lines are present, the

 Structural unit one or two, preferably two, bonds to

 adjacent structural units on. If three dotted lines are present in the formulas, the structural unit has one, two or three, preferably two, bonds to adjacent structural units. If four dashed lines are present in the formulas, the structural unit has one, two, three or four, preferably two, bonds to adjacent structural units. They can be arranged independently, identically or differently, in ortho, meta or para position.

Group 2 structural units having electron injection and / or electron transport properties are, for example, pyridine, Pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline,

Anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives, but also triarylboranes and other O, S or N-containing heterocycles.

It may be preferred if the polymers according to the invention comprise units from group 3 in which structures which increase hole mobility and which electron mobility increase (ie units from groups 1 and 2) are directly bonded to one another or contain structures which both the hole mobility and the

Increase electron mobility. Some of these units can serve as emitters and shift the emission color to green, yellow or red. Their use is thus suitable, for example, for the production of other emission colors from originally blue-emitting polymers.

Group 4 structural units are those which are also included in

Room temperature with high efficiency from the triplet state can emit light, so show electrophosphorescence instead of electrofluorescence, which often causes an increase in energy efficiency. Compounds which contain heavy atoms with an atomic number of more than 36 are suitable for this purpose. Preference is given to compounds which contain d- or f-transition metals which contain the o. G. Fulfill condition. Particular preference is given here to corresponding structural units which contain elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). As structural units for the polymers according to the invention, e.g. various complexes, such as e.g. in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2. Corresponding monomers are used in the

WO 02/068435 A1 and described in WO 2005/042548 A1.

Group 5 structural units are those which improve the singlet to triplet state transition and which, assisting with the Group 4 structural elements, improve the phosphorescence properties of these structural elements. In particular, carbazole and bridged carbazole dimer units are suitable for this purpose, as described, for example, in WO 2004/070772 A2 and WO 2004/1 3468 A1 to be discribed. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds, as described, for example, in WO 2005/040302 A1.

Structural units of group 6 are, in addition to those mentioned above, those which have at least one further aromatic or another conjugated structure which is not classified under the above-mentioned. Fall groups, d. H. which only slightly influence the charge carrier mobility, the none

organometallic complexes are or which do not affect the

Have singlet-triplet transition. Such structural elements can influence the emission color of the resulting polymers. Depending on the unit, they can therefore also be used as emitters. Aromatic structures having from 6 to 40 carbon atoms or else toluenes, stilbene or bisstyrylarylene derivatives which may each be substituted by one or more radicals R are preferred. Particularly preferred is the incorporation of 1, 4 or 9,10-anthrylene, 1, 6, 2,7 or 4,9-pyrenylene, 3,9 or 3,10-perylenylene, 4, 4'-tolanylene, 4,4'-stilbenylene, benzothiadiazole and corresponding oxygen derivatives, quinoxaline, phenothiazine,

Phenoxazine, dihydrophenazine, bis (thiophenyl) arylene,

Oligo (thiophenylene), phenazine, rubrene, pentacene or

Perylene derivatives, which are preferably substituted, or preferably conjugated push-pull systems (systems containing donor and

Acceptor substituents) or systems such as squarins or quinacridones, which are preferably substituted.

Group 7 structural units are units containing aromatic structures having from 6 to 40 carbon atoms, which are typically used as a backbone polymer. These are, for example, 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9'-spirobifluorene derivatives, phenanthrene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzooxepine derivatives and cis- and trans-indenofluorene derivatives but also 1, 2, 1, 3 or 1, 4-phenylene, 1, 2, 1, 3 or 1, 4-naphthylene, 2,2'-, 3,3'- or 4, 4'-biphenylylene, 2,2 ", 3,3" or 4,4 "-terphenyls, 2,2 ', 3,3' or 4,4'-bi-1,1 '-naphthylylene or 2,2 "', 3,3"' or 4,4 "'quarterphenylylene derivatives. Preferred structural units from group 7 are the structural units of the following formulas (7a) to (7o):

where R, k, m, n and p can assume the meanings given above.

In the formulas (7a) to (7o), the dashed lines represent possible bonds to the adjacent structural units in the polymer. If two dashed lines are present in the formulas, then the

Structural unit one or two, preferably two, bonds to

adjacent structural units on. If four or more dashed lines are present in the formulas (formulas (7g), (7h) and (7j)), the structural units have one, two, three or four, preferably two, bonds to adjacent structural units. They can be arranged independently, identically or differently, in ortho, meta or para position.

Group 8 structural units are those which affect the film morphology and / or the rheological properties of the polymers, e.g. Siloxanes, alkyl chains or fluorinated groups, but also particularly rigid or flexible units, liquid-crystalline units or crosslinkable groups.

Preference is given to polymers according to the invention which, in addition to structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX), additionally additionally contain one or more units selected from Groups 1 to 8. It may likewise be preferred if more than one further structural unit from a group is present at the same time.

Preferred polymers according to the invention are those which have, in addition to at least one structural unit of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) still contain units from group 7. It is likewise preferred if the polymers according to the invention

 Contain units that improve the charge transport or the charge injection, ie units from the group 1 and / or 2.

It is also particularly preferred if the inventive

 Contain polymer structural units from group 7 and units from group 1 and / or 2.

The polymers according to the invention are either homopolymers of structural units of the formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII) or (IX) 10 or copolymers. The polymers of the invention may be linear or branched, preferably linear. Copolymers of the invention may in addition to one or more structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) potentially one or several other structures from the groups 1 to 8 listed above.

The copolymers according to the invention can have random, alternating or block-like structures or alternatively have several of these structures in turn. The copolymers according to the invention particularly preferably have random or alternating structures.

 More preferably, the copolymers are random or alternating copolymers. How to obtain copolymers with block-like structures

and which further structural elements are particularly preferred for this purpose are described in detail, for example, in WO 2005/014688 A2

 described. This is via quote part of the present application. It should also be emphasized once again that the polymer can also have dendritic structures.

 25

 In a further embodiment of the present invention, the polymers according to the invention contain, in addition to one or more

 Structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) and, if appropriate, further structural units selected from the abovementioned groups 1 to 8 at least one,

Preferably a structural unit having a crosslinkable group Q. "Crosslinkable group Q" in the sense of the present invention means a functional group which is able to undergo a reaction and thus form an insoluble compound, the reaction being able to react with another, identical group Q, another, different group Q. or any other part of it or another

Polymer chain done. The crosslinkable group is thus a reactive group. As a result of the reaction of the crosslinkable group, a correspondingly crosslinked compound is obtained. The chemical reaction can also be carried out in the layer, resulting in an insoluble layer. The crosslinking can usually be assisted by heat or by UV, microwave, X-ray or electron radiation, if appropriate in the presence of an initiator. "Insoluble" in the sense of the present invention preferably means that the polymer according to the invention after the crosslinking reaction, ie after the reaction the crosslinkable groups, at room temperature in an organic solvent having a solubility which is at least a factor of 3, preferably at least a factor of 10, lower than that of the corresponding non-crosslinked polymer of the invention in the same organic solvent.

The structural unit bearing the crosslinkable group Q may in a first embodiment be selected from the structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII) , (VIII) and / or (IX).

Preferred structural units bearing the crosslinkable group Q are the following, from the structural units of the formulas (I-1a), (1-1b), (1-1c) and (1-1d), respectively, of the structural units of the Formulas (Xla), (Xlb), (Xlc) and (Xld):

(XIa) where Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Q, R, n, r and X can assume the meanings indicated above,

o, s, t, u and v are each 0 or 1, and the sum (o + s +

t + u + v) = 1, 2, 3, 4 or 5; preferably 1, 2 or 3; more preferably 1 or 2, and most preferably 1.

When the sum is 2, preferably (o + v) = 2 or (s + v) = 2. When the sum is 1, preferably o = 1, s = 1 or v = 1, more preferably s = 1 or v = 1.

wobei Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, Q, R, n, r und X die oben angegebenen Bedeutungen annehmen können,

where Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Q, R, n, r and X can assume the meanings indicated above,

o, s, t, u, v, w and x are each 0 or 1, and the sum (o + s + t + u + v + w + x) = 1, 2, 3, 4, 5, 6 or 7; preferably 1, 2, 3 or 4; more preferably 1, 2 or 3, and most preferably 1 or 2.

When the sum is 2, it is preferable that (o + x) = 2, (t + v) = 2 or (s + w) = 2.

 When the sum is 1, preferably o = 1, s = 1, u = 1, w = 1 or x = 1, more preferably s = 1, u = 1 or w = 1.

wobei Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, Q, R, k, n, p, q und X die oben (XIc)

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Q, R, k, n, p, q and X are as above

 can assume given meanings,

 o, s, t, u, v and w are each 0 or 1, and the sum (o + s +

 t + u + v + w) = 1,2,3,4,5 or 6, preferably 1,2,3 or 4, more preferably 1, 2 or 3, and most preferably 1 or 2.

When the sum is 2, it is preferable that (o + w) = 2, (s + w) = 2,

 (t + w) = 2, (u + w) = 2 or (o + v) = 2.

 When the sum is 1, o = 1, s = 1, t = 1, v = 1 or w = 1 are preferably o = 1 s = 1, t = 1 or w = 1.

wobei Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶, Q, R, k, n, p, q und X die oben

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Q, R, k, n, p, q and X are as above

 can assume given meanings,

 o, s, t, u, v, w, x, y and z are each 0 or 1, and the sum (o + s + t + u + v + w + x + y + z) = 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 1, 2, 3 or 4, more preferably 1, 2 or 3 and most preferably 1 or 2.

When the sum is 2, preferably (o + z) = 2, (s + x) = 2,

 (t + y) = 2, (o + w) = 2 or (u + w) = 2

 When the sum is 1, o = 1, s = 1, t = 1, v = 1, x = 1, y = 1 or z = 1 are preferably o = 1, s = 1, t = 1, v = 1, x = 1, y = 1 or z = 1.

Analogously, the structural units of the formula (IV), (V), (VI) and (VII) can also have crosslinkable groups Q. Furthermore, in a second embodiment, the structural unit bearing the crosslinkable group Q may be selected from the structural units disclosed in Groups 1-8.

A preferred structural unit bearing the crosslinkable group Q is the following structural unit of the formula (XII) derived from the triarylamine units of group 1:

wobei Ar¹ , Ar² und Ar³ die oben in Bezug auf Formel (I) angegebenen Bedeutungen annehmen können.

wherein Ar ¹ , Ar ² and Ar ^{3 may have} the meanings given above in relation to formula (I).

Examples of preferred structural units of the formula (XII) are shown in the following table:

Another preferred structural unit bearing the crosslinkable group Q is the following group 7-derived structural unit of the formula (XIII):

Q

-Ar - (XIII) where Ar ¹ can assume the meanings given in relation to the structural unit of the formula (I).

Examples of preferred structural units of the formula (XIII) are shown in the following table:

As described above, the crosslinkable group Q is a functional group capable of undergoing a chemical reaction to form an insoluble polymeric compound. It is generally possible to use all groups Q known to the person skilled in the art for this purpose. In particular, it is the task of this group to link the polymeric compounds according to the invention, if appropriate with further reactive polymeric compounds, by means of a crosslinking reaction. This results in a crosslinked compound or, when the reaction is carried out in one layer, to a crosslinked layer. A crosslinked layer in the sense of the present invention is understood to mean a layer which can be obtained by carrying out the crosslinking reaction from a layer of the crosslinkable, polymeric compound according to the invention. The

Crosslinking reaction can generally be effected by heat and / or by UV, microwave, X-ray or electron radiation and / or by the use of radical formers, anions, cations, acids and / or Photoacids are initiated. Likewise, the presence of

Catalysts be useful or necessary. Preferably, the

Crosslinking Reaction for which no initiator and no

Catalyst must be added.

Crosslinkable groups Q preferred in accordance with the invention are those in the

The following groups are listed: a) End-stage or cyclic alkenyl or terminal dienyl and alkynyl groups:

 Suitable units are a terminal or cyclic double bond, a terminal dienyl group or a

containing terminal triple bond, in particular terminal or cyclic alkenyl, terminal dienyl or terminal alkynyl groups having 2 to 40 carbon atoms, preferably having 2 to 10 carbon atoms, wherein also individual CH ₂ groups and / or individual H atoms the above groups R can be replaced. Furthermore, groups which are to be regarded as precursors and which are suitable in situ for the formation of a double or

 Triple bond are able. b) alkenyloxy, dienyloxy or alkinyloxy groups:

 Also suitable are alkenyloxy, Dienyloxy- or

 Alkynyloxy groups, preferably alkenyloxy groups.

Acrylsäureqruppen:

 Also suitable are acrylic acid units in the broadest sense, preferably acrylic esters, acrylamides, methacrylic esters and

Methacrylamides. Particularly preferably Ci _-10 alkyl acrylate and C 1 ₀ alkyl methacrylate.

The crosslinking reaction of the groups mentioned above under a) to c) can be carried out via a radical, a cationic or an anionic mechanism but also via cycloaddition. It may be useful to add a suitable initiator for the crosslinking reaction. Suitable initiators for free-radical crosslinking are, for example, dibenzoyl peroxide, AIBN or TEMPO. Suitable initiators for the cationic crosslinking are, for example, AICI ₃ , BF ₃ , triphenylmethyl perchlorate or tropylium hexachloroantimonate. Suitable initiators for the anionic crosslinking are bases, in particular

Butyl lithium.

In a preferred embodiment of the present invention, however, the crosslinking is carried out without the addition of an initiator and is exclusively thermally initiated. This preference is based on the fact that the absence of the initiator prevents contamination of the layer, which could lead to a deterioration of the device properties. d) Oxetanes and oxiranes:

 Another suitable class of crosslinkable groups Q are oxetanes and oxiranes, which crosslink cationically by ring opening.

It may be useful to have a suitable initiator for the

 Add crosslinking reaction. Suitable initiators are

for example, AICI ₃ , BF ₃ , triphenylmethyl perchlorate or

 Tropyliumhexachlorantimonat. Likewise, photoacids can be added as initiators. e) silanes:

Also suitable as a class of crosslinkable groups are silane groups SiR ₃ , where at least two groups R, preferably all three groups

R is Cl or an alkoxy group having 1 to 20 carbon atoms.

 This group reacts in the presence of water to form an oligo- or polysiloxane. f) cyclobutane groups

The above-mentioned crosslinkable groups Q are generally known to those skilled in the art, as are the suitable reaction conditions used to react these groups. Preferred crosslinkable groups Q include alkenyl groups of the following formula Q1, dienyl groups of the following formula Q2,

Alkynyl groups of the following formula Q3, alkenyloxy groups of the following formula Q4, dienyloxy groups of the following formulas Q5,

Alkynyloxy groups of the following formula Q6, acrylic acid groups of the following formulas Q7 and Q8, oxetane groups of the following formulas Q9 and Q10, oxirane groups of the following formula Q 1 and

Cyclobutane groups of the following formula Q12:

0 H_2X

0 H _2X

/ CH ₂

Ζ ₂ Κ ^r11

 Q1 1 Q12

The radicals R ¹¹ , R ² and R ³ in the formulas Q1 to Q8 and Q1 1 in each occurrence, identical or different, is H, a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms , The radicals R ¹¹ , R ¹² and R ¹³ are particularly preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably H or methyl. The indices used have the following meaning: s = 0 to 8; and t = 1 to 8.

The dashed bond in the formulas Q1 to Q11 and the dashed bonds in the formula Q12 represent the attachment of the crosslinkable group to the structural units.

The crosslinkable groups of the formulas Q1 to Q12 may be linked directly to the structural unit, or indirectly, via a further, mono- or polycyclic, aromatic or heteroaromatic

Ring system Ar ¹⁰ as shown in the following formulas Q13 to Q24:

wobei Ar¹⁰ in den Formeln Q13 bis Q24 die gleichen Bedeutungen annehmen kann wie Ar¹.

where Ar ¹⁰ in the formulas Q 13 to Q 24 can assume the same meanings as Ar ¹ .

Particularly preferred crosslinkable groups Q are the following:

The radicals R ¹¹ and R ² in the formulas Q7a and Q13a to Q19a in each occurrence, identical or different, are H or a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radicals R ¹ and R ¹² are particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably methyl.

The radical R ¹³ in the formulas Q7b and Q19b at each occurrence is a straight-chain or branched alkyl group having 1 to 6 C atoms, preferably 1 to 4 C atoms. The radical R ³ is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl and very particularly preferably methyl. The indices used have the following meaning: s = 0 to 8 and t = 1 to 8.

 Very particularly preferred crosslinkable groups Q are the following:

In the preferred groups Q1 to Q24, in the particularly preferred groups Q1a to Q24a and in the most preferred groups Q1 b to Q24c, the dashed lines represent the bonds to the

In this context, it should be noted that groups Q12, Q12a, Q12b, and Q24 each have two bonds to two having adjacent ring carbon atoms of the structural unit. All other crosslinkable groups merely have a bond to the structural unit.

The proportion of crosslinkable structural units in the polymer is in the range from 0.01 to 50 mol%, preferably in the range from 0.1 to 30 mol%, particularly preferably in the range from 0.5 to 20 mol% and very particularly preferably in the range from 1 to 15 mol% based on 100 mol% of all the copolymerized monomers contained in the polymer as structural units.

The polymers according to the invention comprising structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) are generally prepared by polymerization of one or more types of monomer, of which at least one monomer in the polymer to

Structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX). Suitable polymerization reactions are the

Known and described in the literature. Particularly suitable and preferred polymerization reactions which lead to C-C or C-N linkages are the following:

(A) SUZUK polymerization;

 (B) YAMAMOTO polymerization;

 (C) SILENT polymerization;

 (D) Heck polymerization;

 (E) NEGISHI polymerization;

 (F) SONOGASHIRA polymerization;

 (G) HIYAMA polymerization; and

 (H) HART IG-BUCHWALD polymerization

How the polymerization can be carried out by these methods and how the polymers can then be separated off from the reaction medium and purified is known to the person skilled in the art and in the literature, for example in WO 03/048225 A2, WO 2004/037887 A2 and WO 2004 / 037887 A2 described in detail. The CC linkages are preferably selected from the groups of the SUZUKI coupling, the YAMAMOTO coupling and the STILLE coupling; the CN linkage is preferably a HARTWIG-BUCHWALD coupling.

The present invention thus also provides a process for the preparation of the polymers according to the invention, which is characterized

characterized in that it is produced by polymerization according to SUZUKI,

Polymerization according to YAMAMOTO, polymerization according to SILENCE or polymerization according to HARTWIG-BUCHWALD.

For the synthesis of the polymers according to the invention, the

corresponding monomers of the formula (MI) are required,

 Y

wobei Ar¹, Ar², Ar³, Ar⁴ und Ar⁵ die in Bezug auf die Struktureinheit der Formel (I) angegebenen Bedeutungen annehmen kann.

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ may assume the meanings given in relation to the structural unit of the formula (I).

The monomers of the formulas (MI-1) and (MI-2) which lead to structural units of the formula (1-1) or (I-2) in the polymers according to the invention are compounds which are correspondingly substituted and to two

Positions have suitable functionalities that allow to incorporate this monomer unit in the polymer. These monomers of the formulas (MI-1) and (Ml-2) are thus also the subject of the present invention. The group Y represents, for one or the other, one for one Polymerization reaction suitable leaving group, so that the incorporation of the monomer units in polymeric compounds is made possible.

Preferably, Y represents a chemical functionality which is identically or differently selected from the class of halogens, O-tosylates, O-triflates, O-sulfonates, boric acid esters, partially fluorinated silyl groups,

Diazonium groups and organotin compounds.

The backbone of the monomer compounds can be functionalized by standard methods, for example by Friedel-Crafts alkylation or acylation. Furthermore, the skeleton can be after

Halogenate standard methods of organic chemistry. The halo- genated compounds can optionally be further implemented in additional functionalization steps. For example, the

halogenated compounds are used either directly or after conversion into a boronic acid derivative or organotin derivative as starting materials for the reaction to polymers, oligomers or dendrimers.

The methods mentioned are merely a selection of the reactions known to the person skilled in the art which, without being inventive, can be used for the synthesis of the compounds according to the invention.

The polymers of the invention can be used as a pure substance, but also as a mixture together with any other polymeric, oligomeric, dendritic or low molecular weight substances. In the present invention, a low molecular weight substance is understood as meaning compounds having a molecular weight in the range from 100 to 3000 g / mol, preferably 200 to 2000 g / mol. These other substances may e.g. improve the electronic properties or self-emit. The mixture referred to above and below as a mixture containing at least one polymeric component. In this way, one or more polymer layers consisting of a mixture (blend) of one or more inventive

Polymers having a structural unit of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and / or (IX) and optionally one or more others Polymers are prepared with one or more low molecular weight substances.

Another object of the present invention is thus a polymer blend comprising one or more polymers of the invention, and one or more further polymeric, oligomeric, dendritic and / or low molecular weight substances.

The invention further provides solutions and formulations of one or more polymers of the invention or a polymer blend in one or more solvents. How such solutions can be prepared is known to the person skilled in the art and described, for example, in WO 02/072714 A1, WO 03/019694 A2 and the literature cited therein.

These solutions can be used to prepare thin polymer layers, for example, by area-coating methods (e.g., spin-coating) or by printing methods (e.g., ink-jet printing).

Polymers containing structural units which have a crosslinkable group Q are particularly suitable for the production of films or coatings, in particular for the production of structured

Coatings, for example by thermal or light-induced in situ polymerization and in situ crosslinking, such as in situ UV photopolymerization or photopatterning. In this case, both corresponding polymers can be used in pure substance, but it is also possible to use formulations or mixtures of these polymers as described above. These can be used with or without the addition of solvents and / or binders. Suitable materials, methods and devices for the methods described above are described, for example, in WO 2005/083812 A2. Possible binders are, for example, polystyrene, polycarbonate, poly (meth) acrylates, polyacrylates, polyvinyl butyral and similar, optoelectronically neutral polymers. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -Fenchone, 1, 2,3,5-tetramethylbenzene, 1, 2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4 Dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol,

Benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,

Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,

Methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene,

Heptylbenzene, octylbenzene, 1, 1-bis (3,4-dimethylphenyl) ethane or

Mixtures of these solvents.

Another object of the present invention is thus the

Use of a polymer containing structural units having a crosslinkable group Q to produce a crosslinked one

Polymer. The crosslinkable group, more preferably one

Vinyl group or alkenyl group is preferably incorporated into the polymer by the WITTIG reaction or a WITTIG analogous reaction. If the crosslinkable group is a vinyl group or alkenyl group, the crosslinking can take place by free-radical or ionic polymerization, which can be induced thermally or by radiation.

Preferably, the free-radical polymerization which is thermally induced is preferably at temperatures of less than 250 ° C, more preferably at temperatures of less than 200 ° C.

Optionally, an additional styrenic monomer is added during the crosslinking process to achieve a higher degree of crosslinking. Preferably, the proportion of styrene monomer added is in the range of 0.01 to 50 mol%, particularly preferably 0.1 to 30 mol%, based on 100 mol% of all the copolymerized monomers contained in the polymer as structural units. The present invention thus also provides a process for producing a crosslinked polymer which comprises the following steps:

(a) providing polymers containing structural units having 5 or more crosslinkable groups Q; and

 (b) Radical or ionic crosslinking, preferably radical crosslinking, which can be induced both thermally and by radiation, preferably thermally.

The crosslinked polymers produced by the process according to the invention are insoluble in all common solvents. In this way, defined layer thicknesses can be produced, which are also due to the

 Application of subsequent layers can not be solved again or dissolved.

The present invention thus also relates to a crosslinked polymer obtainable by the aforementioned method. The crosslinked polymer is preferably prepared in the form of a crosslinked polymer layer as described above. On the surface of such a crosslinked polymer layer, due to the insolubility of the crosslinked polymer in all solvents, another layer of a solvent can be applied by the techniques described above.

The present invention also includes so-called hybrid devices in which one or more layers which are processed from solution and layers which are produced by vapor deposition of low molecular weight substances may occur.

 25

 The polymers according to the invention can be used in electronic or optoelectronic devices or for their preparation.

Another object of the present invention is thus the

30 Use of the polymers of the invention in electronic or optoelectronic devices, preferably in organic

Electroluminescent devices (OLED), organic field effect Transistors (OFETs), organic integrated circuits (O-ICs), organic thin-film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPCs) , particularly preferably in organic electroluminescent devices (OLED).

In the case of the aforementioned hybrid device, combined PLED / SMOLED (Polymer Light Emitting Diode / Small Molecule Organic Light Emitting Diode) systems are used in conjunction with organic electroluminescent devices.

How OLEDs can be produced is known to the person skilled in the art and is described in detail, for example, as a general method in WO 2004/070772 A2, which is to be adapted accordingly for the individual case.

As described above, the polymers according to the invention are very particularly suitable as electroluminescent materials in OLEDs or displays produced in this way.

As Elektrolumineszenzmatenalien in the context of the present invention apply materials that can be used as the active layer. Active layer means that the layer is able to emit light upon application of an electric field (light-emitting layer) and / or that it improves the injection and / or the transport of the positive and / or negative charges (charge injection or

Charge transport layer).

A preferred subject of the present invention is therefore also the use of the polymers according to the invention in OLEDs, in particular as electroluminescent material. The present invention furthermore relates to electronic or optoelectronic components, preferably organic electroluminescent devices (OLED), organic field-effect transistors (OFETs), organic integrated circuits (O-ICs), organic

Thin film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices, and organic photoreceptors (OPCs), more preferably organic electroluminescent devices, having at least one active layer one of these active

Layers one or more polymers of the invention contains. The active layer may, for example, be a light-emitting layer, a charge-transport layer and / or a charge-injection layer.

In the present application text and also in the examples below, the main aim is the use of the polymers according to the invention in relation to OLEDs and corresponding displays. Despite this limitation of the description, it is possible for the skilled person without further inventive step, the polymers of the invention as semiconductors for the other, described above

Uses in other electronic devices.

The following examples are intended to illustrate the invention without it

limit. In particular, the features, properties and advantages of the defined compounds underlying the example in question are also applicable to other, not detailed, but falling within the scope of the claims

Compounds, unless otherwise stated elsewhere.

Examples:

Part A: Synthesis of the monomers

All syntheses are carried out in an argon atmosphere and in dry solvents, unless otherwise described.

A1 Preparation of precursors

A1.1 Preparation of 3-chloro-3,7-dimethyloctane

100 ml (522 mmol) of 3,7-dimethyloctanol (CAS 78-69-3) are initially charged, admixed with 0.2 ml (2 mmol) of pyridine and cooled to -5 ° C. 45.6 ml (628 mmol) of thionyl chloride are added dropwise with stirring so that the temperature does not exceed 5 ° C. Resulting HCl and S0 ₂ gas is driven with an argon stream from the apparatus and discharged through a scrubbing tower. After the addition is stirred for 2 h, then the cooling is removed and stirred for 12 h. About a Vigreux column (about 10 cm in length) is initially distilled off at room temperature under reduced pressure excess thionyl chloride. Then the product is fractionally distilled at 2 mbar and a head temperature of 60-65 ° C. This gives 88.9 g (96% of theory) of the product as a colorless oil.

A1.2 Preparation of the Alkylated Aromatics Alk1 to Alk3

The preparation of alkylated aromatics takes place by means of a Friedel-Crafts reaction in accordance with methods A and B described below by way of example.

Method A:

613 g Biphenyl (3.975 mol) werden in 2.5 I Dichlormethan gelöst und mit 24.5 g (0.15 mol) Eisen(lll)chlorid versetzt. Bei Raumtemperatur werden unter kräftigem Rühren 1227 ml f-Butylchlorid (11.130 mol) innerhalb von 3 h zugetropft. Entstehendes HCI-Gas wird dabei mit einem Argon-Strom aus der Apparatur getrieben und über einen Waschturm abgeleitet. Nach vollständiger Zugabe wird die Mischung für 4 h zum Rückfluß erhitzt. Dann wird die Heizung entfernt und für weitere 12 h nachgerührt. Die Mischung wird über etwa 750 g Kieselgel filtriert, das mit etwa 500 ml Dichlormethan nachgewaschen wird. Die gelbe Lösung wird am Rotationsverdampfer vollständig vom Lösungsmittel befreit, der verbleibende orangefarbene Fest- Stoff wird mit etwa 2 I Ethanol bei 60°C ausgerührt. Die Mischung wird für 1 h auf 0°C abgekühlt, dann wird der Feststoff abgesaugt und zweimal mit je 300 ml kaltem Ethanol gewaschen. Nach Trocknen im Vakuumtrocken- schrank verbleiben 827 g (78% der Theorie) als hellgelber kristalliner Feststoff. Alkylation with f-butyl chloride to 4,4'-di-i-butylbiphenyl (Alk1)

613 g of biphenyl (3.975 mol) are dissolved in 2.5 l of dichloromethane and admixed with 24.5 g (0.15 mol) of iron (III) chloride. At room temperature, 1227 ml of f-butyl chloride (11,130 mol) are added dropwise with vigorous stirring within 3 h. Resulting HCI gas is driven with an argon stream from the apparatus and discharged through a scrubbing tower. After complete addition, the mixture is heated to reflux for 4 h. Then the heater is removed and stirred for another 12 h. The mixture is filtered through about 750 g of silica gel, which is washed with about 500 ml of dichloromethane. The yellow solution is completely freed from solvent on a rotary evaporator, the remaining orange solid is stirred with about 2 l of ethanol at 60 ° C. The mixture is cooled to 0 ° C. for 1 h, then the solid is filtered off with suction and washed twice with 300 ml of cold ethanol each time. After drying in a vacuum oven, 827 g (78% of theory) remain as a pale yellow crystalline solid.

Method B:

 Alkylation with 3-chloro-3,7-dimethyloctane to give di (3,7-dimethyloctan-3-yl) biphenyl (Alk2)

24.7 g (160 mmol) of biphenyl and 26.0 g (160 mmol) of iron (III) chloride are initially charged without solvent, mixed with a KPG stirrer. While cooling with an ice bath 85.0 g (480 mmol) of 6-chloro-3,7-dimethyl-octane are added dropwise within 30 min, the mixture is increasingly better stirrable. Resulting HCI gas is driven out of the apparatus with an argon stream and discharged through a scrubbing tower. After complete addition is stirred for 4 h and then treated with about 100 ml of heptane. The suspension is filtered through about 30 g of silica gel, which is washed with about 500 ml of heptane. The pale yellow solution is completely freed from solvent on a rotary evaporator, leaving a yellow oil. This is over a distillation bridge without cooling at 10 ^"2 mbar and a head temperature of up to 170 ° C of excess 3-chloro-3,7-dimethyioctane and monosubstituted biphenyl freed.

 Optionally, even small amounts of unreacted biphenyl can crystallize in the bridge. In the bottom remain 54.9 g (79% of theory as a mixture of isomers) as a yellow oil.

GC-MS analysis of Alk2 shows three compounds in the ratio of about 60: 35: 5 area percent of the peaks in the GC with the expected mass for the product. NMR spectroscopy and the intermediate tertiary carbocations during alkylation make the following substitution patterns likely (stereoisomers are neglected).

Therefore, below the illustrated do-alkyl substituents are representative of the possible isomers and / or their mixtures in any percentage composition.

In a similar way fluorene can be alkylated to Alk3:

A1.3 Preparation of Bromides Bröl to Bro5

A1.3.1 Bromination of the Compounds Alk1 to Alk3 Preparation of 2-bromo-4,4'-di-f-butylbiphenyl (bromo)

54.9 g (126 mmol) of 4,4'-di-f-butylbiphenyl are dissolved in 120 ml. 12.9 ml (253 mmol) of bromine in 40 ml of dichloromethane are added dropwise at room temperature with stirring over 15 min, during which the mixture begins to boil. It is heated to reflux for 3 h. Then the mixture is cooled to 0 ° C and treated with vigorous stirring with 50 ml of saturated aqueous sodium thiosulfate solution and stirred for 15 min. The phases are separated. The organic phase is washed twice with saturated aqueous sodium thiosulfate solution and twice with saturated aqueous sodium bicarbonate solution, dried over sodium sulfate and freed from the solvent on a rotary evaporator. The residue is taken up in 50 ml of heptane and filtered through about 50 g of silica gel, which is washed with 100 ml of heptane. The solvent is removed on a rotary evaporator. The remaining residue is purified in a short path distillation at 10 ^-3 mbar and a gradually increased jacket temperature of up to 180 ° C. This leaves 60.6 g (81% of theory) of a yellowish solid.

In an analogous manner, the bromides Bro2 and Bro3 can be represented:

.2 Herstellung von Bro4

.2 Production of Bro4

4-Bromo-2,7-di-f-butylfluorene (Bro3) can be prepared according to Bull. Chem. Soc. Jpn. 1986, 59, 97-103 are dealkylated to 4-bromofluorene (Bro5):

A1.3.3 Production of Bro5

4-Bromofluorene (Bro4) can be alkylated analogously to Organometallics 2013, 32, 460-467 with 1-iodooctane (CAS 629-27-6) to form 4-bromo-9,9-di-n-octylfluorene (Bro5) , The yield is 87%

A1.5 Preparation of spirobifluorenes Spi1 to Spi3

4-bromo-9,9'-spirobifluorene (Spi1) can be prepared analogously to Organic Letters 2009, 77, 2607-2610 according to the following scheme with a yield of 77% over both stages.

HOAc, HCI conc, 80

 In an analogous process 2 ', 7'-dialkylated 4-bromo-9,9-spirobifluorenes can be prepared by reaction of 4,4'-dialkyl-substituted 2-bromobiphenyl and 4-bromofluorenone, as exemplified by the compounds Spi2 and Spi3 shown:

A1.6 Synthesis of diarylamines ArA1 and ArA2:

A1 .6.1 Synthesis of ArA:

 60.0 g (220 mmol) of Bro5 are dissolved in 0.8 l of dried toluene, 20.5 g (220 mmol) of aniline and 42 g (0.44 mol) of sodium fe / f-butoxide are added successively and the solution is saturated with nitrogen. 1 .8 g (2.2 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) are added and the reaction mixture is stirred under reflux for 24 hours. The solid is filtered off and washed with toluene. The filtrates are concentrated and columned on silica gel with a mixture of toluene-heptane: 1-1 as the eluent. Then the solvent is removed on the rotary evaporator as far as possible and the residue in the final

Dryed vacuum oven. There remain 51.4 g (82% of theory) as a viscous oil.

A1.6.2 Synthesis of ArA 2:

50.0 g (126 mmol) of Spi1 are dissolved in 0.5 l of dried toluene, 1.8 g (126 mmol) of aniline and 24.3 g (253 mmol) of sodium FeAf-butoxide are added successively and the solution is saturated with nitrogen. 1.0 g (1 .2 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) are added and the reaction mixture is stirred at reflux for 24 hours. The solid is filtered off and washed with toluene. The filtrates are concentrated, stirred hot with ethanol, and recrystallized in ethyl acetate. The solid is filtered off and dried in a vacuum oven. There remain 40.2 g (78% of theory) as a white solid. A1.6 Preparation of Triarylamines Mol. A, Mo4.A, M06.A, M0II .A, Mo13.A and Mo15.A

Method A:

30.0 g (34.9 mmol) of 2,8-dibromo-6,6,12,12-tetraoctyl-6,12-dihydro-indeno [1,2-b] fluorene are dissolved in 0.3 l of dried toluene, 18.1 g

 (72.6 mmol) biphenyl-2-yl-phenyl-amine (CAS 35887-50-4), 36.7 g

 (11 1 mmol) cesium carbonate and 0.32 g (1.4 mmol) of palladium (II) acetate are added as a solid successively and the solution is saturated with nitrogen. 2.8 ml (2.8 mmol) of tri-f-butylphosphine solution (1 M in toluene) are added and the reaction mixture is stirred at reflux for 24 hours.

 The solid is filtered off and washed with toluene. The filtrates are concentrated, stirred hot with ethanol, filtered off with suction and dried together with the precipitated solid in a vacuum oven. It remains 28.3 g (68% of theory) as a yellow solid.

Method B:

For compounds which are not obtained in sufficient purity even after prolonged stirring with ethanol (up to 24 hours) as a solid or after recrystallization, purification by column chromatography on silica gel (about 20 g per gram of substance) with toluene as the eluent is carried out. guided. Then the solvent is removed on the rotary evaporator as far as possible and finally dried in a vacuum oven.

The following compounds can be prepared analogously to the processes described:

A2. Preparation of the bis-triarylamines according to the invention with 4-bromophenyl radicals Mo1.Br, Mo4.Br, M06.Br, Mo11.Br, Mo13.Br, Mo15.Br Method A: Preparation of Mo1.Br

28.3 g (23 mmol) of 2,8-di [(biphenyl-2-yl) -phenyl-amino] -6,6,12,12-tetraoctyl-6H, 12H-indeno [1,2-b] fluorene (Mo1 .A) are dried in 0.7 l

Dissolved tetrahydrofuran (THF) and cooled to 0 ° C. 8.5 g (47 mmol) of N-bromo-succinimide are added in portions as a solid and the solution is stirred at 20.degree. C. for 14 hours.

The reaction mixture is concentrated. The residue is stirred hot in ethanol. The solid is filtered and recrystallized three times in ethyl acetate (0.8 L each). After sucking off the solid and drying in a vacuum drying oven, it is tempered at 10 ^{~ 5} mbar and 180 ° C. to remove residues of solvents and volatile impurities. This gives 22.0 g (71% of theory) of the product as a yellow powder with a purity of 99.8% by HPLC.

Method B:

For compounds which are not obtained in sufficient purity even after prolonged stirring with ethanol (up to 24 h) as a solid or after recrystallization, a column chromatographic purification over silica gel (about 20 g per gram of substance) with toluene as the eluent. Then the solvent is removed on the rotary evaporator as far as possible and finally annealed at 10 ^"5 mbar and 180 ° C to remove residues of solvents and volatile impurities.

The following compounds can be prepared analogously to the processes described:

A3. Preparation of bis-triarylamines according to the invention having 4-pinacolato borananyl-phenyl radicals mol .Bo, Mo.sub.4.Bo, M.sub.6.B0, Mo.sub.11.Bo, Mo.sub.13.Bo, M.sub.105.B.sub.0

Method A: Preparation of Mol. Bo

22.0 g (16.3 mmol) of 2,8-di [(biphenyl-2-yl) - (4-bromophenyl) -amino] -6,6,12,12-tetraoctyl-6H, 12H-indeno [1,2-b ] fluorene (Mo1.Br), 8.8 g (35 mmol)

 Bis (pinacolato) diborane and 8.0 g (82 mmol) of potassium acetate are placed in 200 ml of dioxane. The mixture is saturated with argon, with 0.38 g

(0.69 mmol) 1, 1'-bis (diphenylphosphino) ferrocene and 0.15 g (0.69 mmol) palladium (II) acetate and heated to reflux for 14 h. To

Cool to room temperature, filter over about 50 g of Celite and remove the solvent on a rotary evaporator as much as possible. The remaining dark brown residue is taken up in about 150 ml of heptane and stirred vigorously for 3 h. After aspiration, the solid is extracted from two nested extraction tubes in a continuous hot extractor without adsorbent with about 200 ml of heptane for about 16 h. After cooling to room temperature, the solid is filtered off with suction and the mother liquor is concentrated to dryness on a rotary evaporator. Both solids are combined and taken up in about 150 ml of heptane. The suspension is heated to reflux and added dropwise until complete toluene solution (about 40 ml). After cooling to room temperature, the solid formed is filtered off with suction and recrystallized again as described. After sucking off the solid and drying in

This is tempered ⁵ mbar and 200 ° C at 10 ^"in order to remove residues of solvents and volatile impurities vacuum drying cabinet. There remain 11.7 g (50% of theory) as a yellow solid with a purity of 99.8% by HPLC.

Method B:

For compounds which, even after prolonged stirring with heptane (up to 24 h) not as a solid or after recrystallization is not sufficient Purity is obtained, a column chromatographic purification over silica gel (about 20 g per gram of substance) with toluene as the eluent. Then the solvent is removed on the rotary evaporator as far as possible and finally the residue at 10 ^"5 mbar and 180 ° C annealed to remove residues of solvents and volatile

Remove impurities.

The following compounds can be prepared analogously to the processes described:

A4. Preparation of the other monomers used Mo7.Bo, Μοδ.Βο, Mo9.Br, Mo9.Bo, Mo12.Br, Mo12.Bo and Mo16.Bo

A4.1 Preparation of 3,3'-bis (pinacolato borananyl) biphenyl (Mo7.Bo)

100.0 g (321 mmol) of 3,3'-dibromo-1,1'-biphenyl (CAS 16400-51 -4), 244.2 g of bis (pinacolato) diborane (963 mmol), 125.8 g (1.3 mol) of potassium acetate) and 5.24 g (6 mmol) of 1,1-bis (diphenylphosphino) ferrocene-dichloropalladium (II) are heated in 1 l of tetrahydrofuran with vigorous stirring for 2 days to reflux. The reaction mixture is filtered through Celite at room temperature. The solvent is removed in vacuo, the remaining solid recrystallized in acetonitrile. The resulting solid is filtered off, dried in vacuo and then sublimed at 140 ° C and a pressure of 10 ^"5 mbar. This gives 55.7 g (43% of theory) of the product as a colorless powder having a purity of 99.7% by HPLC.

A4.2 Production of M08.Br

Stage 1: Preparation of M08.A

50.7 g (100 mmol) of Spi 2, 16.9 g (100 mmol) of diphenylamine and 14.4 g (150 mmol) of sodium f-butoxide are suspended in 0.4 l of toluene. The

Mixture is saturated with argon, treated with 2 ml (2 mmol) of tri-f-butylphosphine (1 M in toluene) and 0.2 g (1 mmol) of palladium (II) acetate and heated to reflux for 6 h. After cooling to room temperature, solid components are filtered off; The organic phase is washed three times with 100 ml of water, dried over sodium sulfate and freed from solvent on a rotary evaporator. The remaining solid is stirred twice with 50 ml of heptane for 30 min, filtered off and dried in a vacuum drying oven. There remain 54.8 g (92% of theory) as a beige solid. Stage 2: Preparation of Mo8.Br

54.8 g (92 mmol) of M08.A are initially charged in 600 ml of THF and cooled to 0 ° C. Then with vigorous stirring in portions 32.7 g (84 mmol) / V-bromosuccinimide are added as a solid so that the

Temperature of the mixture does not exceed 5 ° C. The cooling is removed and the mixture stirred for a further 12 h. The solvent is dissolved on

Rotary evaporator completely removed. The residue is dissolved in about 350 ml of toluene, filtered through alumina (basic, activity level 1) and again concentrated to dryness on a rotary evaporator. The remaining solid is recrystallized three times from about 1 L of heptane. Residues of succinimide are removed by multiple warm stirring of the solid with ethanol. After suction filtration and drying in a vacuum desiccator this is washed twice at 10 ^"5 mbar and 270 ° C fractionated sublimated. There remain 43.0 g (62% of theory) as a colorless glassy solid with a purity of 99.9% by HPLC.

A4.3 Production of Mo9.Br

Step 1 :

50.0 g (295 mmol) of diphenylamine are mixed with 64.5 g (355 mmol) of 3-bromobenzonitrile, 20 ml (20 mmol) of tri-f-butylphosphine solution (1 M in toluene) 2.65 g (11 mmol) of palladium (II) acetate and 85.2 g (886 mmol) of sodium f-butoxide in 1000 ml of toluene and heated with stirring for 15 hours to reflux. After cooling, the organic phase is washed three times with 1000 ml of water, dried over sodium sulfate and then concentrated in vacuo to dryness. The remaining solid is mixed with about 400 ml of heptane in a continuous

Hot extractor extracted over a bed of alumina (basic, activity level 1). After cooling, the precipitated solid is filtered off, washed twice with about 200 ml of heptane and dried under vacuum. There remain 53.0 g (66% of theory) as a slightly colored solid. Level 2:

53.0 g (196 mmol) of 3-diphenylaminobenzonitrile are dissolved in 500 ml of dry tetrahydrofuran and cooled to 0 ° C. With ice-cooling and vigorous stirring, 69.8 g (392 mmol) / V-bromosuccinimide are added in portions as a solid in such a way that the temperature does not exceed 5 ° C. The cooling is removed and the mixture is stirred for 12 hours. The solvent is removed in vacuo and the remaining solid dissolved in as little ethyl acetate. The solution is washed three times with about 500 ml of aqueous sodium hydroxide solution (5%) and twice with water. The organic phase is concentrated to dryness. There remain 70.8 g (84% of theory) as a colorless solid.

Level 3:

70.8 g (165 mmol) of 3- [bis (4-bromophenyl)] - benzonitrile are dissolved in 700 ml of dry dichloromethane and cooled to -78 ° C. 174 ml (174 mmol) of a 1 M solution of diisobutylaluminum hydride in toluene are added dropwise so that the temperature does not exceed -50 ° C. The cooling is removed, the mixture is allowed to warm to 10 ° C and cooled again to -10 ° C from. After addition of 175 ml of tetrahydrofuran is rapidly mixed with a mixture of 43 g of concentrated sulfuric acid and 175 ml of water and stirred for 12 hours without further cooling. The mixture is with aqueous sodium hydroxide solution neutral. The organic phase is separated, washed twice with about 350 ml of water and once with 350 ml of saturated sodium chloride solution and dried over magnesium sulfate. The solvent is removed on a rotary evaporator. This leaves a yellow oil that crystallizes within 24 hours. The solid is extracted with about 300 ml of heptane in a continuous hot extractor over a bed of alumina (basic, activity level 1) and filtered off after cooling. It is recrystallized three times from isopropanol. After drying in vacuo, 13.0 g (18% of theory) remain as a yellow solid.

A4.4 Production of Mo9.Bo

13.0 g (30 mmol) of 3- [bis (4-bromophenyl) amino] benzaldehyde, 33.7 g (137 mmol) of bis (pinacolato) diborane, 14.8 g (151 mmol) of potassium acetate, 0.27 g (1.2 mmol) of palladium (II) acetate and 0.69 g (1.2 mmol) of bis (diphenylphosphino) ferrocene are heated to reflux in 500 ml of dioxane with vigorous stirring for 14 h. The solvent is removed in vacuo, the remaining solid taken up in as little ethyl acetate as possible and filtered through silica gel with a mixture of ethyl acetate and heptane (1: 1). The solvent is removed in vacuo and the remaining oil is stirred with about 100 ml of heptane for 2 hours. The resulting solid is filtered off, dried in vacuo and then at 200 ° C and a pressure of 10 ^"5 mbar fractionated sublimated. This gives 3.5 g (22% of theory) of the product as a colorless powder having a purity of 99.8% according to HPLC , A4.5 Preparation of Mo12.Br

71.5 g of N4, N4'-bis-biphenyl-4-yl-N4, N4'-diphenyl-biphenyl-4,4'-diamine (12 mmol) (CAS: 134008-76-7) are dissolved in 1.5 l of dried tetrahydro - Furan (THF) dissolved and cooled to 0 ° C. 40 g of N-bromosuccinimide

 (224 mmol) are added in portions as a solid and the solution stirred at 20 ° C for 14 hours.

The solid is filtered and washed with THF. The filtrates are concentrated together, stirred with water, filtered with suction and in

 Dryed vacuum oven. The residue will be twice in

Recrystallized dimethylformamide (DMF) (700 ml and 500 ml). The solid is then stirred three times with 700 ml of ethanol and then dried in a drying oven. There remain 72.7 g (82% of theory) as a slightly colored solid with a purity of 99.0% by HPLC

A4.6 Production of Mo12.Bo

58.3 g of N4, N4'-bis-biphenyl-4-yl-N4, N4'-bis (4-bromo-phenyl) -biphenyl-4,4'-diamine (73 mmol) are dissolved in 1.5 l of dried THF, 44.5 g

Bis (pinacolato) diboron (175.2 mmol) and 43 g potassium acetate (438 mmol) are added successively as a solid and the solution is saturated with argon. 1 .2 g of 1, 1-bis (diphenylphosphino) ferrocenedichloro-Pd (II) complex is added and the reaction mixture stirred under reflux for 22 hours.

The solid is filtered through silica gel and Celite and the solution is concentrated. The residue is treated with 800 ml of dichloromethane. The phases are separated. The organic phase is washed three times with 300 ml of water and dried over Na ₂ S0 ₄ , then filtered and concentrated by rotary evaporation. The product is filtered through silica gel (toluene as eluent). The clean fractions (about 35 g) are recrystallized from a mixture of 50 ml of heptane and 170 ml of toluene. The solid is filtered, washed with heptane and dried. This gives 33.5 g (52% of theory) of the product as a colorless powder with a purity of 99.1% by HPLC.

A4.7 Preparation of Mo16.Bo Preparation of 2 ', 7'-bis (3,7-dimethyloctan-3-yl) -9,9'-spirobifluorene-4-yl-bis (3-bromophenyl) amine ( M0I6.B0)

Step 1 :

180.0 g (266 mmol) of 4-bromo-2 ', 7'-bis- (3,7-dimethyloctan-3-yl) -9,9'-spirobifluorene (Spi3) are dissolved in 2 l of dried dioxane, 56.2 g (480 mmol) f-butyl carbamate (CAS 4248-19-5), 182.5 g (560 mmol) cesium carbonate and 12.3 g (21.3 mmol) of 4,5-bis (diphenylphosphino) -9,9-dimethyl- xanthene (xantphos) are added as solids gradually, then the solution is saturated with nitrogen. 3.6 g (16 mmol) of palladium (II) acetate are added and the reaction mixture is refluxed for 2 days. stir. The solvent is removed on a rotary evaporator as far as possible and the dark residue is hot-extracted with heptane. The solvent is completely removed on a rotary evaporator and the remaining solid recrystallized in a toluene-heptane mixture (1: 1). The solid is filtered off and dried in a vacuum oven. There remain 119.5 g (63% of theory) as a light yellow solid.

Level 2:

119.0 g (167.2 mmol) of A / - [2 ', 7'-bis- (3,7-dimethyloctan-3-yl) -9,9'-spirobi-fluoren-4-yl] -carbamic acid-f-butyl ester are obtained in Dissolved 500 ml of dried dichloromethane, 51.5 ml (670 mmol) of trifluoroacetic acid are carefully added dropwise. The reaction mixture is stirred for 2 h at room temperature. The reaction mixture is concentrated and the residue is dissolved in 300 ml of toluene. The organic phase is washed twice with 300 ml of NaOH (1 M solution) and then with 400 ml of water. The organic phase is dried over sodium sulfate and freed from the solvent on a rotary evaporator. There remain 96.2 g (94% of theory) as a white solid.

97.8 g (346 mmol) 1-Brom-3-iodbenzol, 96.1 g (157 mmol) 4-Amino-2\7'- bis-(37-dimethyloctan-3-yl)-9,9'-spirobifluoren, 2.4 g (12.6 mmol) Stage 3: Preparation of Mo16.Br

97.8 g (346 mmol) of 1-bromo-3-iodobenzene, 96.1 g (157 mmol) of 4-amino-2'7'-bis- (37-dimethyloctan-3-yl) -9,9'-spirobifluorene, 2.4 g (12.6 mmol)

Copper (I) iodide, 70.4 g (1.26 mol) of potassium hydroxide and 2.27 g (12.6 mmol) of 1, 10-phenanthroline are suspended in 750 mL of o-xylene. The reaction mixture is saturated with argon and stirred at reflux overnight. The mixture is cooled to room temperature and then filtered with toluene over silica gel and alumina and concentrated by rotary evaporation. The light brown solid is sucked off. The solid is then purified by column chromatography (heptane). The product is recrystallized in a heptane-toluene mixture (1: 1). This gives 76.8 g (53% of theory) of the product as a colorless powder with a purity of 99.7% by HPLC.

Stage 4: Preparation of Mo16.Bo:

70.0 g (76 mmol) Mo16.Br, 41.0 g (161 mmol) Bis(pinacolato)diboran und 37.6 g (383 mmol) Kaliumacetat werden in 0.8 I Dioxan vorgelegt. Das Gemisch wird mit Argon gesättigt, mit 1 .75 g (3.22 mmol) 1 ,1 '- Bis(diphenylphosphino)ferrocen und 0.72 g (3.22 mmol) Pa!ladium(ll)acetat versetzt und für 14 h zum Rückfluß erhitzt. Nach Abkühlen auf

70.0 g (76 mmol) of Mo16.Br, 41.0 g (161 mmol) of bis (pinacolato) diborane and 37.6 g (383 mmol) of potassium acetate are initially introduced in 0.8 l of dioxane. The mixture is saturated with argon, combined with 1.75 g (3.22 mmol) of 1,1'-bis (diphenylphosphino) ferrocene and 0.72 g (3.22 mmol) of palladium (II) acetate and heated to reflux for 14 h. After cooling to

 Room temperature is filtered through about 50 g of Celite and the solvent removed on a rotary evaporator as far as possible. The remaining dark residue is taken up in about 700 ml of heptane and stirred vigorously for 3 h, whereby a brown solid precipitates. After aspiration, the solid from two nested extraction sleeves in a continuous hot extractor without adsorbent with about 1000 ml

Heptane extracted for about 16 h. After cooling to room temperature, the solid is filtered off with suction and the mother liquor is concentrated to dryness on a rotary evaporator. Both solids are combined and re-extracted as described; the extraction sleeves used are only weakly colored after the second extraction. The mother liquor is concentrated again to dryness and combined with the precipitated solids. It is taken up in about 250 ml of heptane, the suspension is heated to reflux and added dropwise to complete toluene solution (about 190 ml). After cooling to room temperature, the solid formed is filtered off with suction and recrystallized again as described. After suction filtration of the solid and drying in a vacuum desiccator this is tempered ⁵ mbar and 180 ° C at 10 ^"in order to remove residues of solvents and volatile impurities. There remain 38.7 g (48% of theory) as a colorless glassy solid with a purity of 99.7 % by HPLC.

A2.5 Other monomers

Mo17.Br WO 02/077060 A1 Further monomers for the preparation of the polymers according to the invention are already described in the prior art, are commercially available or are prepared according to the literature procedure and are summarized in the following table:

Mo17.Br WO 02/077060 A1

Part B: Synthesis of Polymers

Preparation of the Comparative Polymers V1 and V2 and the Polymers Pol to Po14 According to the Invention.

The comparative polymers V1 and V2 and the inventive

Polymers Po to Po14 are prepared by SUZUKI coupling according to the method described in WO 2010/097155 from the monomers shown in Part A.

The polymers V1 and V2 and Pol to Pol 5 prepared in this manner contain the structural units after removal of the leaving groups in the percentages indicated in Table 2 (percentages = mol%). In the case of the polymers which are prepared from monomers which have aldehyde groups, these are converted into crosslinkable vinyl groups after the polymerization by means of the WITTIG reaction in accordance with the process described in WO 2010/097155. The polymers listed correspondingly in the following table and used in Part C thus have crosslinkable vinyl groups instead of the aldehyde groups originally present.

The palladium and bromine contents of the polymers are determined by ICP-MS. The determined values are below 10 ppm. The molecular weights M _w and the polydispersities D are determined by means of gel permeation chromatography (GPC) (Model: Agilent HPLC System Series 1100) (column: PL-RapidH from Polymer Laboratories;

Solvent: THF with 0.12% by volume o-dichlorobenzene; Detection: UV and refractive index; Temperature: 40 ° C). Calibration is with polystyrene standards. The results are summarized in the table below.

table

Part C: Device examples

The polymers according to the invention can be processed from solution and, compared to vacuum-processed OLEDs, lead to OLEDs which are much easier to produce and nevertheless have good properties.

 Whether the crosslinkable variants of the polymers according to the invention give a completely insoluble layer after crosslinking is tested analogously to WO 2010/097155.

 Table C1 shows the remaining layer thickness of the original 20 nm according to the washing process described in WO 2010/097155.

If the layer thickness does not decrease, the polymer is insoluble and thus the crosslinking is sufficient.

Table C1:

 Control of the residual layer thickness of originally 20 nm after washing test

As can be seen from Table C1, the comparative polymer V1, which carries no crosslinking group, hardly crosslinks at 220 ° C. The comparative polymer V2 and the inventive polymers Po01, Po02, Po05, Po13 and Po14 completely crosslink at 220 ° C.

The preparation of such solution-based OLEDs has already been described many times in the literature, for example in WO 2004/037887 and WO 2010/097 55. The procedure is adapted to the conditions described below (layer thickness variation, materials).

The polymers of the invention are in two different

Layer sequences used:

Structure A is as follows:

 Substrate,

 - ITO (50 nm),

 PEDOT (80 nm),

 Hole transport layer (HTL) (20 nm),

Emission layer (EML) (60 nm),

 - hole blocking layer (HBL) (10 nm)

 Electron transport layer (ETL) (40 nm),

 - cathode.

Structure B is as follows:

Substrate,

 ITO (50 nm),

 PEDOT (20 nm),

 Hole transport layer (HTL) (40 nm),

 Emission layer (EML) (30 nm),

Electron transport layer (ETL) (20 nm),

 - cathode.

 The substrate used is glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, they are coated with PEDOTPSS. The spin-on takes place in air from water. The layer is baked for 10 minutes at 180 ° C.

PEDOTPSS is procured from Heraeus Precious Metals GmbH & Co. KG, Germany. On these coated glass slides are the

Lochtransport- and the emission layer applied.

As a hole transport layer, the compounds of the invention and comparative compounds are used, each dissolved in toluene. The typical Feststoffgehait of such solutions is about 5 g / l, if, as here, the typical for a device layer thicknesses of 20 or 40 nm means Spincoating is to be achieved. The layers are in one

Inertgasatmosphäre, in this case argon, spin-on and baked for 60 minutes at 180 ° C or 220 ° C.

The emission layer is always composed of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter). Furthermore, mixtures of several matrix materials and co-dopants can occur. An indication such as H1 (92%): Dotand (8%) here means that the material H1 is present in a weight fraction of 92% and the dopant in a weight fraction of 8% in the emission layer. The mixture for the emission layer is dissolved for Structure A in toluene. The typical solids content of such

Solutions is about 18 g / l, if, as here, the typical for a device layer thickness of 60nm is to be achieved by spin coating. The

Layers are spin-coated in an inert gas atmosphere, in this case argon, and baked at 180 ° C. for 10 minutes. In structure B, the emission layer is formed by thermal evaporation in a

Vacuum chamber formed. In this case, the layer may consist of more than one material, the other by co-evaporation in one

be added to certain volume fraction. An indication like

H3: Dotand (95%: 5%) means here that the materials H3 and dopant are present in a volume fraction of 95%: 5% in the layer.

The materials used in the present case are shown in Table C2.

Table C2:

 Structural formulas of the materials used in the emission layer

The materials for the hole blocking layer and electron transport layer are also thermally evaporated in a vacuum chamber and are shown in Table C3. The hole blocking layer consists of ETM1. The electron transport layer consists of the two materials ETM1 and ETM2, which are admixed by co-evaporation in a volume fraction of 50% each. Table C3:

 Used HBL and ETL materials

The cathode is formed by the thermal evaporation of a 100nm thick aluminum layer.

The exact structure of the OLEDs can be found in Table C4. In the column HTL the polymer used is listed, as well as the temperature at which the layer is baked out and optionally crosslinked.

Table C4:

Structure of the OLEDs

Example HTL Structure EML

 composition

Polymer T [° C]

C01 V1 180 ° C B H3 95%; SEB 5%

C02 V2 180 ° C A H1 30%; H2 55%; TEG 15%

C03 PoO3 220 ° C AH1 30%; H2 55%; TEG 15%

C04 Po04 180 ° C B H3 95%; SEB 5%

C05 Po05 220 ° C A H1 30%; H2 55%; TEG 15%

C06 Po10 180 ° CB H3 95%; SEB 5% C07 pole 180 ° CB H3 95%; SEB 5%

C08 Po13 180 ° C A H1 30%; H2 55%; TEG 15%

The OLEDs are characterized by default. For this purpose, the electroluminescence spectra, current-voltage-luminance characteristics (LUL characteristics) are determined assuming a lambertian radiation characteristic and the (operating) life. Key figures are determined from the lUL characteristic curves, such as the operating voltage (in V) and the external quantum efficiency (in%) at a specific brightness. LD50 @ 1000cd / m ² is the lifetime until the OLED has dropped to 50% of the initial intensity, ie 500 cd / m ² , at a starting brightness of 1000 cd / m ² . Accordingly, LD80 @ 0000cd / m ^{2 is} the lifetime until the OLED has dropped to 80% of the initial intensity, ie 8000 cd / m ² , at a starting brightness of 10000 cd / m ² .

The properties of the different OLEDs are summarized in Tables C5 a and b. Examples C01 and C02 are

Comparative examples, all other examples show properties of OLEDs according to the invention.

Tables C5 a-b: Properties of the OLEDs

Table C5 a

Efficiency at Voltage at LD80 at

 example

1000 cd / m ² 1000 cd / m ² 10000 cd / m ²

 % EQE [V] [h]

 C02 17.0 4.2 1 10

 C03 16.6 4.8 240

 C05 18.5 4.5 290

C08 17.2 4.6 270 Table C5 b

As shown in Tables C5 a-b, the polymers according to the invention, when used as hole transport layers in OLEDs, give improvements over the prior art, in particular with regard to service life and operational stress. Green and blue emitting OLEDs are produced with the materials according to the invention.

Claims

claims 1 . Polymer having at least one structural unit of the following formula (I):

10  is there Ar ¹ to Ar ⁵ at each occurrence, each same or different, a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms substituted by one or more R radicals 1 can be; i and j are each 0 or 1, the sum (i + j) = 1; R for each occurrence are identical or different H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= 0) R ¹ , P (= _O ) (R ¹ ) _2l S (= _O ) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C Atoms or one A branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R ¹ , wherein one or more nonadjacent CH ₂ groups is represented by R ¹ C = CR ¹ , C = C, Si (R ¹ ) ₂ , C = O, C = S, C = NR ¹ , P (= O) (R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ can and where one or more H atoms pass through 25 D, F, Cl, Br, I or CN may be replaced, or a mono- or polycyclic, aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic Ring atoms, which may be substituted by one or more radicals R ¹ , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be replaced by one or more R ¹ may be substituted, or a Diarylaminogruppe, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R, or a crosslinkable group Q, wherein two or more radicals R also together with one another mono- or polycyclic, aliphatic, aromatic and / or benzoannelliertes ring system can form; R ¹ in each occurrence is identical or different H, D, F or an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic and / or a heteroaromatic hydrocarbon radical having 5 to 20 C atoms, in which one or more H Atoms can be replaced by F; where two or more substituents R ^{1 can} also together form a mono- or polycyclic, aliphatic or aromatic ring system; and n = 1, 2 or 3, the dashed lines being bonds to adjacent ones Represent structural units in the polymer, characterized in that in the case i = 0 and j = 1, Ar ² and / or Ar ⁴ is in each case substituted in at least one, preferably in one of the two ortho positions, with Ar ⁶ , Ar ^{6 being} a mono- or polycyclic, is aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R and in the case i = 1 and j = 0, Ar ⁴ and / or Ar ^{5 are} each substituted in at least one, preferably in one of the two ortho positions, with Ar ⁶ , wherein Ar ^{6 is} a mono- or polycyclic, aromatic or heteroaromatic Ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals. Polymer according to claim 1, characterized in that the at least one structural unit of the formula (I) is selected from the structural unit of the following formula (1-1):

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and n may have the meanings given in claim 1. Polymer according to claim 1, characterized in that the at least one structural unit of the formula (I) is selected from the structural unit of the following formula (I-2):

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and n may have the meanings given in claim 1. Polymer according to claim 1 or 2, characterized in that the at least one structural unit of the formula (I) or (1-1) is selected from the structural units of the following formulas (1-1 a), (1-1 b), ( I-1c) and (l-1d):

wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and R are as indicated above  To be able to assume meanings  m = 0, 1, 2, 3 or 4,  n = 0, 1, 2 or 3, X = CR _2, NR, SiR _2, O, S, C = 0 or P = 0, and  r = 0 or 1. Polymer according to claim 1 or 2, characterized in that the

 at least one structural unit of the formula (I) or (1-1) is selected from structural units of the following formulas (II), (III), (IV), (V), (VI), (VII), (VIII) and (IX): - -

- - - (II)

wherein Ar ¹ , Ar ³ , Ar ⁵ , Ar ⁶ , R, m, n and X may have the meanings given in claims 1 and 2, and  p = 0, 1, 2, 3, 4 or 5. 6. Polymer according to one or more of claims 1 to 5, characterized in that the proportion of structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII) , (VIII) and / or (IX) in the polymer is in the range of 50 to 95 mol%, based on 100 mol% of all  copolymerizable monomers contained in the polymer as structural units. Polymer according to one or more of claims 1 to 6, characterized in that the polymer in addition to structural units of the formula (I), (II), (III), (IV), (V), (VI), (VII), ( VIII) or (IX) further, different from the structural units of the formulas (I), (II), (III), (IV), (V), (VI), (VII), (VIII) or (IX) Has structural units. Process for the preparation of a polymer according to one or more of Claims 1 to 7, characterized in that it is prepared by polymerization according to SUZUKI, polymerization according to YAMAMOTO, polymerization according to STILLE or polymerization according to HARTWIG-BUCHWALD. 9. A polymer blend comprising one or more polymers according to one or more of claims 1 to 7, which contain at least one structural unit of the formula (I), and one or more further polymeric, oligomeric, dendritic and / or low molecular weight substances. Solutions or formulations of one or more polym according to one or more of claims 1 to 7 or a  The polymer blend of claim 9 in one or more  Solvents. 1 1. Use of a polymer according to one or more of  Claims 1 to 7 in electronic or optoelectronic  Devices, preferably in organic electroluminescent devices (OLED), organic light-emitting  electrochemical cells (OLEC), organic field effect transistors (OFET), organic integrated circuits (O-IC), organic thin film transistors (TFT), organic solar cells (O-SC), organic laser diodes (O-lasers), organic  photovoltaic (OPV) elements or devices or organic photoreceptors (OPC), particularly preferably in organic electroluminescent devices (OLED). Electronic or opto-electronic device, preferably organic electroluminescent devices (OLED), organic light-emitting electrochemical cells (OLEC), organic field-effect transistors (OFET), organic integrated circuits (O-IC), organic thin-film transistors (TFT), organic solar cells (O SC), organic laser diodes (O-lasers), organic  photovoltaic (OPV) elements or devices and organic photoreceptors (OPC), more preferably organic  Electroluminescent devices, having one or more active layers, wherein at least one of these active layers contains one or more polymers according to one or more of claims 1 to 7.